US5138088A - Nitrobenzoyl-3-cyclopropylaminoacrylates and a process for the preparation thereof - Google Patents
Nitrobenzoyl-3-cyclopropylaminoacrylates and a process for the preparation thereof Download PDFInfo
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- US5138088A US5138088A US07/522,174 US52217490A US5138088A US 5138088 A US5138088 A US 5138088A US 52217490 A US52217490 A US 52217490A US 5138088 A US5138088 A US 5138088A
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- United States
- Prior art keywords
- nitrobenzoyl
- formula
- ethyl
- chloro
- fluoro
- Prior art date
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- OJTMOGHSQHRCLX-UHFFFAOYSA-N C1CC1NC([N+]([O-])=O)=C(C(=O)O)C(=O)C1=CC=CC=C1 Chemical class C1CC1NC([N+]([O-])=O)=C(C(=O)O)C(=O)C1=CC=CC=C1 OJTMOGHSQHRCLX-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 11
- 238000002360 preparation method Methods 0.000 title claims description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical compound NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims abstract 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 18
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 13
- 125000001153 fluoro group Chemical group F* 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 125000001246 bromo group Chemical group Br* 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical group COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 3
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 claims description 2
- 101150108015 STR6 gene Proteins 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 3
- 150000007524 organic acids Chemical class 0.000 abstract description 2
- WXGVHRSLYAEQCS-UHFFFAOYSA-N [benzoyl-(2-nitrocyclopropyl)amino] prop-2-enoate Chemical compound [O-][N+](=O)C1CC1N(OC(=O)C=C)C(=O)C1=CC=CC=C1 WXGVHRSLYAEQCS-UHFFFAOYSA-N 0.000 abstract 1
- 239000007858 starting material Substances 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical group 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GSDSWSVVBLHKDQ-UHFFFAOYSA-N 9-fluoro-3-methyl-10-(4-methylpiperazin-1-yl)-7-oxo-2,3-dihydro-7H-[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic acid Chemical class FC1=CC(C(C(C(O)=O)=C2)=O)=C3N2C(C)COC3=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-UHFFFAOYSA-N 0.000 description 2
- -1 benzoyl ester Chemical class 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- VWJSSJFLXRMYNV-UHFFFAOYSA-N 1-(3,4-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(F)C(F)=C1 VWJSSJFLXRMYNV-UHFFFAOYSA-N 0.000 description 1
- SNWRGZXPALLRLB-UHFFFAOYSA-N 2-(4-chloro-5-fluoro-2-nitrobenzoyl)-3-ethoxypent-2-enoic acid Chemical compound CCOC(CC)=C(C(O)=O)C(=O)C1=CC(F)=C(Cl)C=C1[N+]([O-])=O SNWRGZXPALLRLB-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- FPENCTDAQQQKNY-UHFFFAOYSA-N 3,4-difluorobenzoic acid Chemical compound OC(=O)C1=CC=C(F)C(F)=C1 FPENCTDAQQQKNY-UHFFFAOYSA-N 0.000 description 1
- HGGRAOYTQNFGGN-UHFFFAOYSA-N 4,5-difluoro-2-nitrobenzoic acid Chemical compound OC(=O)C1=CC(F)=C(F)C=C1[N+]([O-])=O HGGRAOYTQNFGGN-UHFFFAOYSA-N 0.000 description 1
- FRLJGJAJZBNKFA-UHFFFAOYSA-N 4-chloro-5-fluoro-2,3-dinitrobenzoic acid Chemical compound OC(=O)C1=CC(F)=C(Cl)C([N+]([O-])=O)=C1[N+]([O-])=O FRLJGJAJZBNKFA-UHFFFAOYSA-N 0.000 description 1
- GGTQVIUWLUDQKR-UHFFFAOYSA-N 4-chloro-5-fluoro-2-nitrobenzoic acid Chemical compound OC(=O)C1=CC(F)=C(Cl)C=C1[N+]([O-])=O GGTQVIUWLUDQKR-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BAOKLNBWBQPAOC-UHFFFAOYSA-N C=1C(F)=C(F)C=C([N+]([O-])=O)C=1C(=O)C(C(=O)OCC)=CNC1CC1 Chemical compound C=1C(F)=C(F)C=C([N+]([O-])=O)C=1C(=O)C(C(=O)OCC)=CNC1CC1 BAOKLNBWBQPAOC-UHFFFAOYSA-N 0.000 description 1
- JTRUCTOQISXRPY-UHFFFAOYSA-N OC(=O)CC(=O)C1=CC(F)=C(F)C=C1[N+]([O-])=O Chemical compound OC(=O)CC(=O)C1=CC(F)=C(F)C=C1[N+]([O-])=O JTRUCTOQISXRPY-UHFFFAOYSA-N 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- UBMGCVUYOULEEX-UHFFFAOYSA-N [(4-chloro-5-fluoro-2-nitrobenzoyl)-(2-ethylcyclopropyl)amino] prop-2-enoate Chemical compound CCC1CC1N(OC(=O)C=C)C(=O)C1=CC(F)=C(Cl)C=C1[N+]([O-])=O UBMGCVUYOULEEX-UHFFFAOYSA-N 0.000 description 1
- RLVWAMDIMGJJCA-UHFFFAOYSA-N acetyl 4-chloro-3-ethyl-5-fluoro-2-nitrobenzoate Chemical compound CCC1=C(Cl)C(F)=CC(C(=O)OC(C)=O)=C1[N+]([O-])=O RLVWAMDIMGJJCA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910000435 bromine oxide Inorganic materials 0.000 description 1
- 238000000160 carbon, hydrogen and nitrogen elemental analysis Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SYJKPYFOVXKFIS-UHFFFAOYSA-N ethyl 2-(4,5-difluoro-2-nitrobenzoyl)-3-ethoxyprop-2-enoate Chemical compound CCOC=C(C(=O)OCC)C(=O)C1=CC(F)=C(F)C=C1[N+]([O-])=O SYJKPYFOVXKFIS-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- IOVGROKTTNBUGK-SJCJKPOMSA-N ritodrine Chemical compound N([C@@H](C)[C@H](O)C=1C=CC(O)=CC=1)CCC1=CC=C(O)C=C1 IOVGROKTTNBUGK-SJCJKPOMSA-N 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/30—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and unsaturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
Definitions
- the present invention relates to nitrobenzoyl-3-cyclopropylaminoacrylates of the formula (I) and the preparation process thereof. ##STR1## wherein
- R methyl, ethyl or propyl
- X halogen (chloro, fluoro or bromo)
- Nitrobenzoyl-3-cyclopropylaminoacrylates of the formula (I) are the good intermediate for the preparation of quinolon derivatives (IV) with strong sterilization effect for bacteria (antibacterial agent). ##STR2## wherein
- X halogen (chloro, fluoro or bromo)
- the first stage is to prepar nitrobenzoyl-3-alkoxyacrylates of the formula (III), which can be obtained by reacting nitrobenzoylester compound of the formula (II) with alkylorthoformate in organic acid solvent and the second one is to prepare nitrobenzoyl-3-cyclopropylaminoacrylates of the formula (I), which can be obtained by reacting nitrobenzoyl-3-alkoxyacrylates of the formula (III) and cyclopropylamine.
- R methyl, ethyl or propyl
- R methyl, ethyl or propyl
- X halogen (chloro, fluoro or bromo)
- the benzoyl ester derivatives of formula II are prepared by reacting 5-fluoro-4-halo-2-nitrobenzoic acid with a chlorinating agent, such as thionyl chloride or trichlorophosphorous, followed by reacting the acid chloride so formed with a dialkylmalonate.
- a chlorinating agent such as thionyl chloride or trichlorophosphorous
- the 4,5-difluoro-2-nitrobenzoic acid starting material can be prepared by nitration in mixed acid of 3,4-difluorobenzoic acid, which is obtained by oxidation 3,4-difluoroacetophenone.
- the 4- chloro-5-fluoro-2-nitrobenzoic acid starting material can be obtained by the following process:
- nitrobenzoyl-3-alkoxyacrylates of the formula (III) can be obtained by refluxing the acetic acid anhydrous solution of nitrobenzoyl ester compound of the formula (II) and ethyl or methylorthoformate for 1 to 5 hours.
- the equivalent ratio between alkylorthoformate and nitrobenzoylester compound of the formula (II) is preferably from 1.2 to 1.5.
- Nitrobenzoyl-3-cyclopropylaminoacrylates of the formula (I) are prepared by adding cyclopropylamine to nitrobenzoyl-3-alkoxyacrylates of the formula (III), then stirring 18°-30° C. for 1 hour wherein the equivalent ratio between cyclopropylamine and nitrobenzoyl-3-alkoxyacrylate is preferably from 1.2 to 1.5.
- This example is the synthetic process of nitrobenzoyl-3-cyclopropylaminoacrylate of the formula (I) from the compound of the formula (II).
- the reactants were refluxed for about 2 hours.
- the starting compound was the compound of the formula III wherein X is chloro and R is ethyl.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Nitrobenzoyl-3-cyclopropylaminoacrylates are prepared by two stage reaction: a) The first stage is the synthesis of nitrobenzoyl-3-alkoxyacrylates from nitrobenzoylester compound and alkylorthoformate in organic acid solvent. b) The second stage is the synthesis of nitrobenzoyl-3-cyclo propylamino acrylate from nitrobenzoyl-3-alkoxyacrylates and cyclopropylamine.
Description
This is a division of application Ser. No. 321,971, filed Mar. 10, 1989, now U.S. Pat. No. 4,965,396.
The present invention relates to nitrobenzoyl-3-cyclopropylaminoacrylates of the formula (I) and the preparation process thereof. ##STR1## wherein
R=methyl, ethyl or propyl
X=halogen (chloro, fluoro or bromo)
Nitrobenzoyl-3-cyclopropylaminoacrylates of the formula (I) are the good intermediate for the preparation of quinolon derivatives (IV) with strong sterilization effect for bacteria (antibacterial agent). ##STR2## wherein
X=halogen (chloro, fluoro or bromo)
The process for the preparation of nitrobenzoyl-3-cyclopropylaminoacrylates of the formula (I) consists of two stage reactions:
The first stage is to prepar nitrobenzoyl-3-alkoxyacrylates of the formula (III), which can be obtained by reacting nitrobenzoylester compound of the formula (II) with alkylorthoformate in organic acid solvent and the second one is to prepare nitrobenzoyl-3-cyclopropylaminoacrylates of the formula (I), which can be obtained by reacting nitrobenzoyl-3-alkoxyacrylates of the formula (III) and cyclopropylamine. ##STR3## wherein
R=methyl, ethyl or propyl
X=halogen (chloro, bromo or fluoro) ##STR4## wherein
R=methyl, ethyl or propyl
X=halogen (chloro, fluoro or bromo)
The detailed preparation method of nitrobenzoylester compounds of the formula (II) from dihalobenzene is described in the previous patent application Ser. No. 321,972 of the same inventors and assignee filed Mar. 10, 1989 on "Benzoylacetic Ester Derivatives and a Process for the Preparation Thereof", claiming priority from Korean application No. 7342/1988, filed Jun. 17, 1988.
Briefly, the benzoyl ester derivatives of formula II are prepared by reacting 5-fluoro-4-halo-2-nitrobenzoic acid with a chlorinating agent, such as thionyl chloride or trichlorophosphorous, followed by reacting the acid chloride so formed with a dialkylmalonate. The 4,5-difluoro-2-nitrobenzoic acid starting material can be prepared by nitration in mixed acid of 3,4-difluorobenzoic acid, which is obtained by oxidation 3,4-difluoroacetophenone. The 4- chloro-5-fluoro-2-nitrobenzoic acid starting material can be obtained by the following process:
(1) 3,4-dichloroacetophenon is nitrated to form 4,5-dichloro-2-nitroacetophenon.
(2) 4,5-dichloro-2-nitroacetophenon is then reacted with metal fluoride in a polar solvent to form 4-chloro-5-fluoro-2-nitroacetophenon.
(3) 4-chloro-5-fluoro-2-nitroacetophenon is oxidized by treatment with a chromic acid solution or a bromine/sodium hydroxide solution to obtain 4-chloro-5-fluoro-2-nitronitrobenzoic acid.
The nitrobenzoyl-3-alkoxyacrylates of the formula (III) can be obtained by refluxing the acetic acid anhydrous solution of nitrobenzoyl ester compound of the formula (II) and ethyl or methylorthoformate for 1 to 5 hours.
Wherein the equivalent ratio between alkylorthoformate and nitrobenzoylester compound of the formula (II) is preferably from 1.2 to 1.5.
Nitrobenzoyl-3-cyclopropylaminoacrylates of the formula (I) are prepared by adding cyclopropylamine to nitrobenzoyl-3-alkoxyacrylates of the formula (III), then stirring 18°-30° C. for 1 hour wherein the equivalent ratio between cyclopropylamine and nitrobenzoyl-3-alkoxyacrylate is preferably from 1.2 to 1.5.
In order to describe this invention more precisely, we have an example as follows;
This example is the synthetic process of nitrobenzoyl-3-cyclopropylaminoacrylate of the formula (I) from the compound of the formula (II).
In this case, R=ethyl and X=chloro in formula (II), R'=methyl in formula (III) and R=ethyl and X=chloro in formula (I) are confined. ##STR5##
The present invention will now be described in detail with reference to the following examples.
To 3 ml of acetic acid anhydrous were added 3 g (0.01 mol) of ethyl (4,5-difluoro-2-nitrobenzoylacetate and 2.44 g (0.016 mol) of ethylorthoformate.
The reactants were refluxed for about 2 hours.
The reaction product after removing the solvent under reduced prtessure of 10 mmHg was directly used for the next reaction without nay purification.
A solution of 0.65 g (0.012 mol) of cyclopropylamine was added dropwisely to the compound of the formula (III), wherein X is fluoro and R is ethyl, at 0° C. prepared in Example 1.
After stirring the reactants at 20°±2° C. for 15 min, 2.95 g (yield 87%, wt %), of solid product could be obtained after filtration and drying process.
mp: 123°-125° C.
NMR (CDCl3)ppm: 11.0 (1H, s), 8.76 (1H, d), 7.95-8.23 (1H, q), 6.92-7.33 (1H, q), 3.83-4.23 (2H, q), 2m76-3.33 (1H, m), 0.79-1.03 (7H, m)
IR(KBr): 1685, 1620, 1530, 1410, 1350 cm-1
CHN analysis for C15 H14 F2 N2 O5 calculated value: C63.82, H6.78, N8.23., observed value: C63.79, H6.90, N8.14.
ethyl-(4-chloro-5-fluoro-2-nitrobenzoyl)-3-ethoxyacrylate (III, X=chloro, R=ethyl)
The procedure of example 1 was repeated while varying the starting compound and the product was obtained. The starting compound was ethyl-4-chloro-5-fluoro-2-nitrobenzoyl acetate (II, X=chloro, R=ethyl)
The procedure of example 2 was repeated while varying the starting compound and the solid products was obtained (yield 71%, wt %).
The starting compound was the compound of the formula III wherein X is chloro and R is ethyl.
NMR(CDCl3)ppm: 8.15-8.60 (2H, m), 7.20 (1H, d), 3.80-4.20 (2H, q), 2.75-3.35 (1H, m), 0.77-1.01 (7H, m)
Claims (4)
1. A process for the preparation of nitrobenzoyl-3-cyclopropylaminoacrylate of the formula (I) comprising:
a first stage for the synthesis of nitrobenzoyl-3-alkoxyacrylate of the formula (III), which is prepared by reacting nitrobenzoylester compound of the formula (II) with alkylorthoformate in acetic acid anhydrous; and
a second stage for the synthesis of nitrobenzoyl-3-cyclopropylaminoacrylate of the formula (I), which is prepared by reacting nitrobenzoyl-3-alkoxyacrylate of the formula (III) with cyclopropylamine, ##STR6## wherein R is methyl, ethyl or propyl and x is chloro, fluoro or bromo, ##STR7## wherein R is methyl, ethyl or propyl and x is chloro, fluoro or bromo, ##STR8## wherein R is methyl, ethyl or propyl and x is chloro, fluoro or bromo and R' is ethyl.
2. The process of claim 1, wherein the first stage reactant is methylorthoformate or ethylorthoformate.
3. The process of claim 1, wherein the first stage reflux time is about 1 to about 5 hours.
4. The process of claim 1, wherein the second stage reaction temperature is about 18° to 30° C. and reaction time is within 1 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/522,174 US5138088A (en) | 1988-06-17 | 1990-05-10 | Nitrobenzoyl-3-cyclopropylaminoacrylates and a process for the preparation thereof |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR7381/1988 | 1988-06-17 | ||
| KR1019880007341A KR910003634B1 (en) | 1988-06-17 | 1988-06-17 | Nitrobenzoyl-3-cyclopropyl aminoacrylate and there of method |
| US07/321,971 US4965396A (en) | 1988-06-17 | 1989-03-10 | Nitrobenzoyl-3-cyclopropylaminoacrylates and a process for the preparation thereof |
| US07/522,174 US5138088A (en) | 1988-06-17 | 1990-05-10 | Nitrobenzoyl-3-cyclopropylaminoacrylates and a process for the preparation thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/321,971 Division US4965396A (en) | 1988-06-17 | 1989-03-10 | Nitrobenzoyl-3-cyclopropylaminoacrylates and a process for the preparation thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5138088A true US5138088A (en) | 1992-08-11 |
Family
ID=27348547
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/522,174 Expired - Fee Related US5138088A (en) | 1988-06-17 | 1990-05-10 | Nitrobenzoyl-3-cyclopropylaminoacrylates and a process for the preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US5138088A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4695646A (en) * | 1985-01-16 | 1987-09-22 | Bayer Aktiengesellschaft | Aminoacrylic acid derivatives |
| US4699992A (en) * | 1984-09-29 | 1987-10-13 | Bayer Aktiengesellschaft | 3-amino-2-benzoylacrylic acid derivatives |
| US4711898A (en) * | 1982-06-14 | 1987-12-08 | Nippon Shinyaku Co., Ltd. | 4-quinolone derivatives having anti-inflammatory, anti-allergic, antitussive, expectorant and antithrombotic activity |
-
1990
- 1990-05-10 US US07/522,174 patent/US5138088A/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4711898A (en) * | 1982-06-14 | 1987-12-08 | Nippon Shinyaku Co., Ltd. | 4-quinolone derivatives having anti-inflammatory, anti-allergic, antitussive, expectorant and antithrombotic activity |
| US4699992A (en) * | 1984-09-29 | 1987-10-13 | Bayer Aktiengesellschaft | 3-amino-2-benzoylacrylic acid derivatives |
| US4695646A (en) * | 1985-01-16 | 1987-09-22 | Bayer Aktiengesellschaft | Aminoacrylic acid derivatives |
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